EP0584625B1 - Esters de l'acide acrylique substitués par une pyridyloxy - Google Patents
Esters de l'acide acrylique substitués par une pyridyloxy Download PDFInfo
- Publication number
- EP0584625B1 EP0584625B1 EP93112732A EP93112732A EP0584625B1 EP 0584625 B1 EP0584625 B1 EP 0584625B1 EP 93112732 A EP93112732 A EP 93112732A EP 93112732 A EP93112732 A EP 93112732A EP 0584625 B1 EP0584625 B1 EP 0584625B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- alkyl
- halogen
- formula
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002148 esters Chemical class 0.000 title claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title 1
- 125000005554 pyridyloxy group Chemical group 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 185
- -1 phenoxy, benzyl Chemical group 0.000 claims description 94
- 125000000217 alkyl group Chemical group 0.000 claims description 78
- 229910052736 halogen Inorganic materials 0.000 claims description 64
- 150000002367 halogens Chemical class 0.000 claims description 64
- 125000005843 halogen group Chemical group 0.000 claims description 61
- 125000001188 haloalkyl group Chemical group 0.000 claims description 60
- 239000002253 acid Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 36
- 125000003545 alkoxy group Chemical group 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 17
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 10
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 10
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 125000000109 phenylethoxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])O* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001035 methylating effect Effects 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 241000607479 Yersinia pestis Species 0.000 claims 5
- 239000005864 Sulphur Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 241000196324 Embryophyta Species 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 15
- 239000004480 active ingredient Substances 0.000 description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 10
- 201000010099 disease Diseases 0.000 description 10
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 125000002877 alkyl aryl group Chemical group 0.000 description 7
- 244000052769 pathogen Species 0.000 description 7
- 229920000151 polyglycol Polymers 0.000 description 7
- 239000010695 polyglycol Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- 241000736122 Parastagonospora nodorum Species 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000011081 inoculation Methods 0.000 description 6
- 230000001717 pathogenic effect Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 6
- 0 CC1=CCCC(OC(C(*)=O)=C)=N1 Chemical compound CC1=CCCC(OC(C(*)=O)=C)=N1 0.000 description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 241000228453 Pyrenophora Species 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000371644 Curvularia ravenelii Species 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- 241001330975 Magnaporthe oryzae Species 0.000 description 4
- 241000233622 Phytophthora infestans Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 241001617088 Thanatephorus sasakii Species 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 241000228452 Venturia inaequalis Species 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 description 4
- 125000004995 haloalkylthio group Chemical group 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000190150 Bipolaris sorokiniana Species 0.000 description 3
- 241001480061 Blumeria graminis Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000520648 Pyrenophora teres Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
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- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
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- 238000011534 incubation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- MRWFLWCUQWXKNH-UHFFFAOYSA-N 6-(4-chlorophenyl)-1h-pyridin-2-one Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC(=O)N1 MRWFLWCUQWXKNH-UHFFFAOYSA-N 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SDSMZSUWTYFEBO-UHFFFAOYSA-M tributyl(methyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](C)(CCCC)CCCC SDSMZSUWTYFEBO-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Definitions
- the present invention relates to new pyridyloxy-acrylic acid esters, a process for their preparation and their use as pesticides.
- the compounds of the formula (I) can be in the form of geometric isomers.
- the invention relates to both the isomer mixtures and the individual isomers.
- the new pyridyloxy-acrylic acid esters of the formula (I) are very suitable as pesticides. They can be used in particular against microorganisms harmful to plants.
- the pyridyloxy-acrylic acid esters of the formula (I) according to the invention have a significantly better activity than plant 1- (6-phenyl-pyrid-2-yl-thio) -2-methoxy-acrylic acid methyl ester, 1- [N-methyl-N - (6-phenyl-pyrid-2-yl) amino] -2-methoxy-acrylic acid methyl ester and 1- [5- (4-chlorophenyl) pyrid-3-yl-oxy] -2-methoxy-acrylic acid methyl ester, which is structurally obvious, known compounds of the same direction of action
- Examples of substances according to the invention are the pyridyloxy-acrylic acid esters listed in the following table.
- 6-aryl-2-pyridones of the formula (IV) required as starting materials in the preparation of acrylic acid derivatives of the formula (II) by the above process are known or can be prepared by processes known in principle (cf., for example, Chem. Ber. 90 , 711 [1957]; Ber. Dtsch. Chem. Ges. 55 , 359 [1922]; Organic Syntheses Coll. Vol. III, 305 [1955]; Angew. Chem. 88 , 261, [1976]; Helv. Chim Acta 24 , 233E [1941]).
- haloacetic acid esters required as reaction components in the above process for the preparation of acrylic acid derivatives of the formula (II) are generally defined by the formula (V).
- Hal preferably represents chlorine, bromine or iodine.
- the haloacetic acid esters of the formula (V) are known
- the formic acid alkyl esters also required as reaction components are generally defined by the formula (VII).
- R preferably represents methyl or ethyl.
- the alkyl formates of the formula (VII) are known.
- the dialkylformamide derivatives also required as reaction components are generally defined by the formula (VIII).
- R 1 and R 2 independently of one another preferably represent methoxy, ethoxy, dimethylamino or diethylamino.
- R 3 preferably represents methyl or ethyl.
- the dialkylformamide derivatives of the formula (VIII) are known.
- All customary strong bases are suitable as acid binders in the reaction of 6-aryl-2-pyridones of the formula (IV) with haloacetic acid esters of the formula (V). Hydrides, such as sodium hydride, can preferably be used.
- reaction temperatures in the above reaction of 6-alyl-2-pyridones of the formula (IV) with haloacetic acid esters of the formula (V) can be varied within a substantial range. In general, temperatures between 50 ° C and 150 ° C.
- All customary strong bases are suitable as acid binders in the reaction of pyridyloxyacetic acid esters of the formula (VI) with formic acid alkyl esters of the formula (VII). Hydrides, such as sodium hydride, can preferably be used.
- reaction temperatures can also be varied within a substantial range in the reaction of pyridyloxyacetic acid esters of the formula (VI) with formic acid alkyl esters of the formula (VII). Generally one works at temperatures between -20 ° C and + 50 ° C.
- reaction temperatures can also be varied within a substantial range in the reaction of pyridyloxyacetic acid esters of the formula (VI) with dialkylformamide derivatives of the formula (VIII). In general, temperatures between -20 ° C and + 150 ° C.
- reaction temperatures can also be varied within a substantial range in the reaction of 2-dialkylaminoacrylic acid derivatives of the formula (IX) with water. In general, temperatures between 0 ° C and + 120 ° C.
- reaction components in the above process for the preparation of acrylic acid derivatives of the formula (II) are each used in approximately equimolar amounts. However, it is also possible to use one or the other component in excess.
- the processing is carried out according to the usual methods.
- the methylating agents required as reaction components when carrying out the process according to the invention are generally defined by the formula (III).
- A preferably represents halogen, optionally substituted alkylsulfonyloxy, optionally substituted alkoxysulfonyloxy or optionally substituted arysulfonyloxy.
- the methylating agents of the formula (III) are generally known compounds of organic chemistry.
- Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons are preferably usable, such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide or sulfoxides, such as
- Dimethyl sulfoxide Dimethyl sulfoxide.
- the process according to the invention can also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst.
- Such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C 13 / C 15 -alkylammonium chloride, trimethyl-C 13 / C 15 -alkylammonium bromide, dibenzyl-dimethyl- 12 -ammonium-ammonium-ammonium-ammonium-bromide 14- alkyl-benzylammonium chloride, dimethyl-C 12 / C 14 -alkyl-benzylammonium bromide, ammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2-methoxyethoxy) ethyl
- the process according to the invention is preferably carried out in the presence of an acid binder.
- All conventional inorganic or organic bases are suitable as such.
- Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, can preferably be used.
- Potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooonane (diazabicyclooonane) (DBN) or diazabicycloundecene (DBU).
- reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -30 ° C and + 120 ° C, preferably at temperatures between -20 ° C and + 60 ° C.
- the process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
- 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, of methylating agent of the formula (III) and, if appropriate, 1.0 are generally employed per mol of acrylic acid derivative of the formula (II) to 5.0 moles, preferably 1.0 to 2.5 moles of acid binder. It is possible to prepare the acrylic acid derivatives of the formula (II) required as starting compounds for carrying out the process according to the invention in a preceding reaction directly in the reaction vessel and then to carry them out further without isolation according to the process according to the invention (one-pot variant). The reaction, work-up and isolation of the reaction products is carried out by known processes (see, for example, DE-OS 39 04 931 or the preparation examples).
- the end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.
- the characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy ( 1 H-NMR).
- the active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms.
- the active ingredients are suitable for use as pesticides in crop protection, in particular as fungicides.
- Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
- the active compounds according to the invention can be used with particularly good results in combating cereal diseases, for example against the pathogen of the real one Powdery mildew on wheat or barley (Erysiphe graminis) or against the causative agent of barley mesh spot disease (Pyrenophora teres) or against the pathogen causing brown spot disease on barley or wheat (Cochliobolus sativus) or against the pathogen causing brown furs in wheat (Leptosphaeria nodor) of fusarioses (Fusarium species) or to combat diseases in fruit and vegetable cultivation, such as against the pathogen of tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or against powdery mildew in fruit and vegetable cultivation or for combat rice diseases, such as against the causative agent of rice speckle disease (Pyricularia oryzae) or against the causative agent of rice stalk disease (Pellicularia sa
- the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist formulations.
- formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
- extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- organic solvents can, for example, also be used as auxiliary solvents.
- liquid solvents aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and the like their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water;
- Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
- Solid carrier materials are suitable: for example natural rock powders
- Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
- Other additives can be mineral and vegetable oils.
- Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
- the formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.
- the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.
- the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules.
- the Application takes place in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or the active ingredient preparation or the active ingredient itself into the soil to inject.
- the seeds of the plants can also be treated.
- the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
- amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
- active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
- the solvent is distilled off, 700 ml of formamide and 70 ml of glacial acetic acid are added to the residue and the mixture is heated at 190 ° C. (bath temperature) for 2 hours.
- 650 ml of water are added to the cooled reaction mixture and extracted 5 times with 300 ml of chloroform each time.
- the combined organic phases are dried and concentrated under reduced pressure.
- the residue is crystallized by stirring with a mixture of 300 ml of ether and 30 ml of ethanol, suction filtered and dried.
- a part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
- the plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.
- Evaluation is carried out 12 days after the inoculation.
- active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
- the plants are placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.
- Evaluation is carried out 10 days after the inoculation.
- the substances according to the invention listed in Examples 1 and 4 show an efficacy of 100% at an active substance concentration of 250 ppm in the spray mixture, while the comparison substance (C) has no effect.
- active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
- the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
- Evaluation is carried out 7 days after the inoculation.
- a part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
- the plants are then placed in an incubation cabin at 20 ° C. and a relative humidity of approx. 100%.
- Evaluation is carried out 3 days after the inoculation.
- a part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
- the plants are then placed in a greenhouse at 25 ° C. and a relative atmospheric humidity of 100%
- the disease infestation is evaluated 4 days after the inoculation.
- the substances according to the invention listed in Examples 1 to 5 show an efficiency of 100% at an active ingredient concentration of 0.025% in the spray mixture, while the comparison substance (C) only has an efficiency of 30%.
- a part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
- the disease infestation is evaluated 5 to 8 days after the inoculation.
- the substances according to the invention listed in Examples 2, 4 and 5 show an efficiency of more than 70% and more at an active ingredient concentration of 0.025% in the spray mixture, while the comparison substance (C) has an efficiency of 30%.
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (10)
- Esters pyridyloxyacryliques de formuleAr représente un groupe aryle contenant de 6 à 10 atomes de carbone, qui peut porter un ou plusieurs substituants identiques ou différents halogéno, hydroxyle, cyano, nitro, alkyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alcoxy à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylthio à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylsulfinyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylsulfonyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, halogénalkyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalcoxy à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylthio à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylsulfinyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylsulfonyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, dialkylamino contenant de 1 à 6 atomes de carbone dans chaque fraction alkyle, alcoxycarbonyle contenant de 1 à 6 atomes de carbone dans la fraction alcoxy, alcoximinoalkyle contenant de 1 à 6 atomes de carbone dans la fraction alcoxy et de 1 à 6 atomes de carbone dans la fraction alkyle, alkylène deux fois lié contenant de 1 à 6 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents, dioxyalkylène contenant de 1 à 6 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, cycloalkyle contenant de 3 à 7 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, hétérocyclyle contenant de 3 à 7 chaînons cycliques, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, et contenant de 2 à 6 atomes de carbone et de 1 à 3 hétéroatomes identiques ou différents tels qu'un atome d'azote, un atome d'oxygène et/ou un atome de soufre, ainsi que les substituants phényle, phénoxy, benzyle, benzyloxy, phényléthyle ou phényléthyloxy, chacun des six substituants mentionnés en dernier lieu pouvant porter, dans la fraction phényle, de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone, alcoxy contenant de 1 à 4 atomes de carbone, halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents, et/ou halogénalcoxy contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents,ouAr représente un groupe hétéroaryle éventuellement benzocondensé contenant de 2 à 9 atomes de carbone et de 1 à 5 hétéroatomes identiques ou différents, chacun de ces radicaux pouvant porter un ou plusieurs substituants identiques ou différents halogéno, hydroxyle, cyano, nitro, alkyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alcoxy à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylthio à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylsulfinyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, alkylsulfonyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone, halogénalkyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalcoxy à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylthio à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylsulfinyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, halogénalkylsulfonyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène identiques ou différents, dialkylamino contenant de 1 à 6 atomes de carbone dans chaque fraction alkyle, alcoxycarbonyle contenant de 1 à 6 atomes de carbone dans la fraction alcoxy, alcoximinoalkyle contenant de 1 à 6 atomes de carbone dans la fraction alcoxy et de 1 à 6 atomes de carbone dans la fraction alkyle, alkylène deux fois lié contenant de 1 à 6 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents, dioxyalkylène contenant de 1 à 6 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, cycloalkyle contenant de 3 à 7 atomes de carbone, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, hétérocyclyle contenant de 3 à 7 chaînons cycliques, portant éventuellement de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone et/ou halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène, et contenant de 2 à 6 atomes de carbone et de 1 à 3 hétéroatomes identiques ou différents tels qu'un atome d'azote, un atome d'oxygène et/ou un atome de soufre, ainsi que les substituants phényle, phénoxy, benzyle, benzyloxy, phényléthyle ou phényléthyloxy, chacun des six substituants mentionnés en dernier lieu pouvant porter, dans la fraction phényle, de 1 à 3 substituants identiques ou différents halogéno, alkyle contenant de 1 à 4 atomes de carbone, alcoxy contenant de 1 à 4 atomes de carbone, halogénalkyle contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents, et/ou halogénalcoxy contenant de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène identiques ou différents, à l'exclusion des composés dans lesquels Ar représente un groupe phényle non substitué et un groupe 2-pyridinyle non substitué.
- Procédé pour la préparation d'esters pyridyloxyacryliques de formuleAr a la signification indiquée à la revendication 1,caractérisé en ce qu'on fait réagir des dérivés d'acide acrylique de formuleE représente un atome d'hydrogène ou un cation de métal alcalin etAr a la signification indiquée ci-dessus,avec des agents de méthylation de formule
CH3-A (III)
dans laquelleA représente un groupe qui s'éloigne, attirant les électrons,éventuellement en présence d'un diluant et éventuellement en présence d'un agent neutralisant les acides, ainsi qu'éventuellement en présence d'un catalyseur. - Agent de lutte contre les parasites, caractérisé par une teneur en au moins un ester pyridyloxyacrylique de formule (I) selon la revendication 1.
- Utilisation d'esters pyridyloxyacryliques de formule (I) selon la revendication 1 pour lutter contre les parasites.
- Procédé pour lutter contre les parasites, caractérisé en ce qu'on répand des esters pyridyloxyacryliques de formule (I) selon la revendication 1, sur les parasites et/ou sur leur biotope.
- Procédé pour la préparation d'agents de lutte contre les parasites, caractérisé en ce qu'on mélange des esters pyridyloxyacryliques de formule (I) selon la revendication 1, avec des diluants et/ou des matières tensioactives.
- Procédé pour la préparation de dérivés d'acide acrylique de formuleAr a la signification indiquée à la revendication 1 etE représente un atome d'hydrogène ou un cation de métal alcalin,caractérisé en ce qu'on fait réagir, dans une première étape, des 6-aryl-2-pyridones répondant à la formuleAr a la signification indiquée ci-dessus,avec des esters halogénacétiques de formule
Hal-CH2-COO-CH3 (V)
dans laquelleHal représente un atome d'halogène,éventuellement en présence d'un diluant et éventuellement en présence d'un agent neutralisant les acides, puis on fait réagir les esters pyridyloxyacétiques ainsi obtenus répondant à la formule (VI)Ar a la signification indiquée ci-dessus,dans une deuxième étape ultérieure, soita) avec des esters alkyliques d'acide formique de formule
H-COOR (VII)
dans laquelleR représente un groupe alkyle,éventuellement en présence d'un diluant ou éventuellement en présence d'un agent neutralisant les acides,
soitb) avec des dérivés de dialkylformamide répondant à la formuleultérieurement avec de l'eau, éventuellement en présence d'un acide,R1 et R2 représentent, indépendamment l'un de l'autre, un groupe alcoxy ou un groupe dialkylamino, etR3 représente un groupe alkyle,éventuellement en présence d'un diluant, puis on fait réagir les dérivés d'acide 2-dialkylaminoacrylique ainsi obtenus répondant à la formule
et on fait réagir les dérivés d'acide acrylique obtenus dans lesquels E représente un atome d'hydrogène, éventuellement avec des hydroxydes de métaux alcalins en présence d'un diluant.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4227748 | 1992-08-21 | ||
DE4227748A DE4227748A1 (de) | 1992-08-21 | 1992-08-21 | Pyridyloxy-acrylsäureester |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0584625A1 EP0584625A1 (fr) | 1994-03-02 |
EP0584625B1 true EP0584625B1 (fr) | 1997-03-26 |
Family
ID=6466085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93112732A Expired - Lifetime EP0584625B1 (fr) | 1992-08-21 | 1993-08-09 | Esters de l'acide acrylique substitués par une pyridyloxy |
Country Status (10)
Country | Link |
---|---|
US (1) | US5580868A (fr) |
EP (1) | EP0584625B1 (fr) |
JP (1) | JPH06199795A (fr) |
KR (1) | KR940003934A (fr) |
CN (1) | CN1089942A (fr) |
BR (1) | BR9303429A (fr) |
DE (2) | DE4227748A1 (fr) |
ES (1) | ES2099331T3 (fr) |
MX (1) | MX9304961A (fr) |
TW (1) | TW242555B (fr) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL115889A0 (en) * | 1994-11-14 | 1996-01-31 | Rohm & Haas | Pyridazinones and their use as fungicides |
US5985919A (en) * | 1995-05-09 | 1999-11-16 | Basf Aktiengesellschaft | (Het)aryloxy-, -thio- , aminocrotonates, methods of preparing them and their use as insecticides and fungicides |
WO2000043354A2 (fr) | 1999-01-22 | 2000-07-27 | Elan Pharmaceuticals, Inc. | Composes inhibant l'adhesion leucocytaire provoquee par vla-4 |
AR035476A1 (es) | 1999-01-22 | 2004-06-02 | Elan Pharm Inc | Compuestos heteroarilo y heterociclicos con anillo fusionado, los cuales inhiben la adhesion de leucocitos mediada por vla-4, composiciones farmaceuticas, el uso de las mismas para la manufactura de un medicamento y un metodo para fijar vla-4 en una muestra biologica |
PL350050A1 (en) * | 1999-01-22 | 2002-10-21 | Elan Pharm Inc | Acyl derivatives which treat vla-4 related disorders |
US6436904B1 (en) * | 1999-01-25 | 2002-08-20 | Elan Pharmaceuticals, Inc. | Compounds which inhibit leukocyte adhesion mediated by VLA-4 |
ATE264298T1 (de) | 1999-03-01 | 2004-04-15 | Elan Pharm Inc | Alpha-aminoessigsäure derivate als alpha 4 beta 7-rezeptor antagonisten |
US7482366B2 (en) * | 2001-12-21 | 2009-01-27 | X-Ceptor Therapeutics, Inc. | Modulators of LXR |
TW200307671A (en) * | 2002-05-24 | 2003-12-16 | Elan Pharm Inc | Heteroaryl compounds which inhibit leukocyte adhesion mediated by α 4 integrins |
TWI281470B (en) * | 2002-05-24 | 2007-05-21 | Elan Pharm Inc | Heterocyclic compounds which inhibit leukocyte adhesion mediated by alpha4 integrins |
AU2006297180A1 (en) | 2005-09-29 | 2007-04-12 | Elan Pharmaceuticals, Inc. | Carbamate compounds which inhibit leukocyte adhesion mediated by VLA-4 |
ATE493405T1 (de) * | 2005-09-29 | 2011-01-15 | Elan Pharm Inc | Pyrimidinylamidverbindungen, die die durch vla-4 vermittelte leukozytenadhäsion inhibieren |
KR20080100271A (ko) * | 2006-02-27 | 2008-11-14 | 엘란 파마슈티칼스, 인크. | Vla-4에 의해 매개되는 백혈구 부착을 억제하는 피리미디닐 술폰아미드 화합물 |
SG10201401836RA (en) * | 2009-04-27 | 2014-10-30 | Elan Pharm Inc | Pyridinone antagonists of alpha-4 integrins |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2557615C2 (de) * | 1975-12-20 | 1985-08-14 | Bayer Ag, 5090 Leverkusen | Neue Niclosamid-Suspensionsformulierungen |
DE3211395A1 (de) * | 1982-03-27 | 1983-09-29 | Hoechst Ag, 6230 Frankfurt | Pyridon-2-derivate, verfahren zu deren herstellung und diese enthaltende arzneimittel |
GB8521082D0 (en) * | 1985-08-22 | 1985-09-25 | Ici Plc | Fungicides |
DE3904931A1 (de) * | 1989-02-17 | 1990-08-23 | Bayer Ag | Pyridyl-substituierte acrylsaeureester |
GB8926429D0 (en) * | 1989-11-22 | 1990-01-10 | Ici Plc | Fungicides |
US5322845A (en) * | 1991-10-02 | 1994-06-21 | Sumitomo Chemical Company, Limited | Acrylic acid derivatives, a fungicide containing them as an active ingredient, and intermediate compounds thereof |
-
1992
- 1992-08-21 DE DE4227748A patent/DE4227748A1/de not_active Withdrawn
-
1993
- 1993-07-23 TW TW082105861A patent/TW242555B/zh active
- 1993-08-09 DE DE59305938T patent/DE59305938D1/de not_active Expired - Fee Related
- 1993-08-09 ES ES93112732T patent/ES2099331T3/es not_active Expired - Lifetime
- 1993-08-09 EP EP93112732A patent/EP0584625B1/fr not_active Expired - Lifetime
- 1993-08-13 US US08/106,248 patent/US5580868A/en not_active Expired - Fee Related
- 1993-08-16 MX MX9304961A patent/MX9304961A/es unknown
- 1993-08-17 JP JP5222749A patent/JPH06199795A/ja active Pending
- 1993-08-19 KR KR1019930016149A patent/KR940003934A/ko not_active Application Discontinuation
- 1993-08-20 BR BR9303429A patent/BR9303429A/pt not_active Application Discontinuation
- 1993-08-21 CN CN93116548A patent/CN1089942A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
JPH06199795A (ja) | 1994-07-19 |
CN1089942A (zh) | 1994-07-27 |
MX9304961A (es) | 1995-01-31 |
EP0584625A1 (fr) | 1994-03-02 |
BR9303429A (pt) | 1994-03-22 |
TW242555B (fr) | 1995-03-11 |
DE4227748A1 (de) | 1994-02-24 |
ES2099331T3 (es) | 1997-05-16 |
DE59305938D1 (de) | 1997-04-30 |
KR940003934A (ko) | 1994-03-14 |
US5580868A (en) | 1996-12-03 |
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